Pesticide-Loaded Nanocarriers from Lignin Sulfonates-A Promising Tool for Sustainable Plant Protection.

Lignin is a promising feedstock in sustainable formulations for agrochemicals not only because of its biodegradability but also because the biopolymer occurs naturally in the cell wall of plants and therefore is renewable and abundant. We used different lignin sulfonates to prepare stable aqueous dispersions of lignin nanocarriers loaded with agrochemicals by interfacial cross-linking in a direct miniemulsion. Despite the differences in structure and functionality, different lignin sulfonates were successfully methacrylated and degrees of methacrylation (>70%) were achieved. The resulting methacrylated lignin sulfonates were water-soluble and exhibited interfacial activity; they were used as reactive surfactants to stabilize oil droplets (cyclohexane or olive or rapeseed oil) loaded with a dithiol cross-linker [EDBET, 2,2'-(ethylenedioxy)bis(ethylthiol)] and a hydrophobic cargo (the fluorescent dye 1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene or the commercial fungicides prothioconazole and pyraclostrobin). After the addition of a water-soluble base, the thia-Michael addition was initiated at the droplet interface and produced lignin sulfonate nanocarriers with a core-shell structure within oily core and a cross-linked shell. Nanocarriers with diameters of ca. 200-300 nm were prepared; encapsulation efficiencies between 65 and 90% were achieved depending on the cargo. When the amount of the cross-linker was varied, the resulting lignin nanocarriers allowed a controlled release of loaded cargo by diffusion over a period of several days. The strategy proves the potential of lignin sulfonates as a feedstock for delivery systems for advanced plant protection.